Novel artificial silk effects and process of producing same



Patented Apr. 23, 1935 I UNITED STATES PATENT OFFICE.

NOVEL ARTIFICIAL SILK EFFECTS AND PROCESS OF PRODUCING SAME Georges Heberlein, Wattwil, Switzerland, as-

signor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application January 13, 1927, Serial No. 161,022. In Germany January 15, 1926 16 Claims. (C1. 8-20) My invention relates to novel artificial silk swelling action. Likewise utilizing a suitable effects and process of producing same. The .obconcentration for the desired effect on a parject of the invention is to provide artificial silk ticular fibre, if the time of treatment is too goods having their physical characteristics long the particular fibre may be destroyed or changed or altered in one or more respects, such spoiled. As is also now understood, variations 5 as a change in the characteristic appearance in temperature of most of the swelling agents and/or hand (touch). I use the term artificial permit of variations in one or both of the other silk in this specification and in the appended factors-concentration and time of treatment. claims as designating the various forms of re- The degree of capability of a swelling treat- 10 generated cellulose such for example as artiment to attack or alter cellulose fibres, I will 10 ficial silks known as viscose, cuprammonium and designate for brevity and convenience herein as nitrocellulose silks, the latter being exemplified, the severity of treatment. For example, if for example, by those known in commerce as sulphuric acid oi say 54 B. is allowed to act Chardonnet & Tubize; and as excluding acetate at a given temperature upon a previously mercersilk. ized cotton fabric for say 5 seconds, and a cer- 15 According to the invention, for example, artitain swelling action is obtained, the severity" ficial silk (regenerated cellulose but not acetate of such treatment will be less than one utilizing silk) may be so treated that the characteristic the sulphuric acid at a concentration of 58 B. excessive lustre of artificial silk fabrics will parand at the same temperature for the same duratially or wholly disappear and the fabric will astion; the severity" of treatment being measured so sume a lustreless, transparent effect, and become by the extent to which the fibres are attacked by stiffer to the touch. As will be more fully exthe treatment. plained according to this invention, a variety Now I have discovered that the character of of novel effects in artificial silk may be obswelling action brought about in the fibres (retained, and some of these effects are especially generated cellulose) is also determined by the 26 valuable in the production of pattern effects on above factors-concentration, time, and temfabrics made entirely or partly of artificial silk perature of the swelling agent, and that swelling fibres. treatments which are of suitable "severity for The process is applicable to artificial silk producing desirable swelling actions on natural 30 goods whether in the form of yarn (threads) or cotton fibre or fabric, are too severe for the 30 fabric (in the piece), and whether the thread or treatment of artificial silk (regenerated celluthe fabric is made entirely or only partly of arlose) and will destroy the same, but that such tificial silk. artificial silk can be successfully treated with The ennobling of cotton fibres by means of swelling agents to produce various desirable perswelling agents is known. It is possible thereby manent effects provided the severity of treat- 35 to impart upon the fibre a lustrous appearance ment with the swelling agent is less than that by mercerization and to produce thereon transcapable of producing any or any substantial parent and/or wool like effects by means of swelling action on the ordinary or natural cotconcentrated acids, according to conditions. ton fibre or fabric.

When cellulosic material such for example as While it is impossible to specify the exact iac- 40 natural cotton fibres or regenerated cellulose is tors, i. e., concentration, time of treatment and acted upon by a swelling agent the swelling actemperature, for every desired effect on the artion or the structural change brought about tificial silk, due to the numerous variety of eiin the fibre is dependent upon certain factors. i. fects that may be desired and the various cone., concentration of the swelling agent and time ditions under which the artificial silk is to be 5 of treatment, and with most swelling agents upon treated, nevertheless, in view of the foregoing the temperature of the agent. This is now well general rule taken in connection with the 3138- known with respect to cotton fibres. If the concific examples of treatments and other informacentration is too low the swelling action will not tion hereinafter given, those skilled in the art take place in a given fibre, no matter how prowill be able to determine the swelling agent and 5 longed the time of treatment may be, and also the desired factors of time, concentration and if the concentration is sufllcient to produce the temperature for the treatment of any particular desired effect on a particular fibre when applied artificial silk (regenerated cellulose) for a parfor a suificient time; if not applied for a sufilticular finish or effect.

cient time there will be no or substantially no According to this invention valuable changes 56 on artificial silk can be produced by means of swelling agents, whereby novel charactexisti not known before on artificial fibres, are obtained. Such swelling agents are: alkali-hydroxide of concentrations as generally used for mercerization, i. e. of a density of above B., sulfuric acid of a density of above 42 B. phosphoric acid of a density of above 50 B., muriatic acid of a density of above B., nitric acid of a density of above 35 B. as well as mixtures of the above-mentioned acids; concentrated salt solutions, 1. e. chloride of zinc solution of a density of above 50 B., calciumrhodanide solution of a density of above B., copperoxideammonia solution with at least 0.3% copper content; but from the commercial standpoint the most desirable of these swelling agents for treating artificial silk are, caustic soda, sulphuric acid, nitric acid and the nitration acid mixtures. Additional substances as proposed for lessening the speed of the reaction can also be added to these agents; among which substances are included one or more univalent and/or muitivalent alcohols heterocyclic bases, formaldehyde and ammonia salts.

in treating artificial silk during longer or shorter periods according to the kind and concentration of the swelling agents, and in conformity with prevailing operating temperatures, the same loses a part of its excessive lustre and, quite in contrast to the reflection of light which is otherwise predominant above everything else, it becomes transparent or translucent; and gradually an effect develops similar to the known transparent or glass like batiste effects on cotton.

If desired, by means of variations in the concentration; temperature and time of action any intermediate grade between the high lustrous character of the original material and the dull, glass-like transparent, stiff, final product can be obtained.

By such treatments, the artificial silk obtains new characteristics unknown before. It has been discovered that just at the beginning of the action, when no extensive swelling has taken place, and hence almost the full lustre is still present, especially in fabrics of artificial silk, an unexpected equalization of the fabric structure takes place, thus causing the unpleasant stripes, which very often appear in artificial silk. to disappear. Also if the swelling of the artificial silk is not continued beyond the permissible measure, then a remarkable increase of the tensile strength is observable; this is due to surface adhesion of the single fibres or filaments.

Each of the mentioned reagents alter artificial silk in a similar manner as above described; that is, they all act to increase the stiffness and translucency of the artificial silk fabric, and many of them to reduce or entirely eliminate the excessive lustre. But in the use of nitrating acid (a composition containing varying proportions of sulphuric and nitric acid with varying aqueous content) widely varying and different effects are produced depending upon the ratio of the nitric acid to the sulphuric acid and upon the aqueous content of the mixture.

For example, if the nitrating acid has an aqueous content below 20%, then quite different effects are produced upon the artificial silk depending upon whether the nitric acid content or the sulphuric acid content predominates. For example if more nitric than sulphuric acid is present the result will be an entirely lustreless non-translucent product; whereas if the sulphuric acid predominates the result will be a voluminous soft rich lustre effect of crepe-like character more nearly like natural silk. But if the nitrating acid contains 20% or more water then regardless of whether the nitric or sulphuric acid predominates, the result is similar to that with the use of the other reagents, i. e., a di minishing of the high lustre and increased stiffness and transparency.

It will thus be seen that one may produce various effects by the use of different mixtures of sulphuric and nitric acids. Such nitrated products may be subsequently treated with known denitrating means to rid them of their ready infiammability.

The manipulation of artificial silk is mostly carried out at normal temperature, but also low temperatures can advantageously be employed, whereas in the use of salt solutions often the warming of agents, some to above the boiling point of water, is necessary. The acting period can be from a few seconds to several minutes, according to the desired effect, in individual cases up to one hour. The fibre material is held loose or under tension in the swelling agents depending upon the effect desired.

The process is applicable to all kinds of artificial silks of regenerated cellulose, but not to acetate silk. They may be treated loose, spun or woven or as a formation of any kind, alone or also mixed with other fibres. Also those fibres, designated as staple fibre, and products obtained by spinning of short single fibres, are susceptible to this ennoblement.

Examples 1. Bleached artificial silk fabrics are passed through caustic alkali of 20 B. for-a period of 4 seconds at normal temperature and slight tension, washed out, soured with diluted sulfuric acid, thoroughly washed and dried. The fabric becomes stiff, translucent, and still exhibits a faint lustre.

2. De-sized artificial silk fabric is passed through a bath cooled to minus 10 C. of sulfuric acid of 49 Be. during 5 seconds, washed completely free from acid and dried. The fabric becomes somewhat stiifer, still snows a high lustre though slightly reduced, has become slightly translucent and appears much more uniform in structure; that is to say, the above-mentioned equalization of the fabric structure is apparent.

3. Immerse artificial silk fabrics at normal temperature during 5 minutes into nitric acid of 40 B. wash out well and dry. The fabric shows a highv lustrous, translucent effect with considerable stiffness of the fabric.

4. Artificial silk yarn is impregnated for a period of 10 minutes in a nitrating acid mixture, consisting of 4 parts sulfuric acid and one part nitric acid with an aqueous content of 7%, then washed and dried. The fibre becomes voluminous, soft, and acquires the rich lustre of real silk.

5. Artificial silk fabrics are passed through a chloride of zinc solution of 67 B. at 40 C. during a period of 10 seconds, washed out and dried. The fabric has become translucent and loses its lustre. Those skilled in the art will observe from a consideration of the foregoing five specific examples of treatments according to the present invention, that in each case the factors of concentration, temperature and duration of treatment are so chosen that the severity of treatment is insufllcient to produce any or any substantial swelling action on natural cotton fibres. Taking for illustration the treatment of Example 1,- while the caustic alkali is of ordinary mercerizin: strength yet the period of treatment is but four seconds at normal temperature as contrasted with the duration of treatment of from 8 to 12 seconds for mercerizing.

If the above named swelling agents are allowed to act upon localized portions of fabrics, which contain artificial silk, these portions are affected, producing contrast between treated and untreated portions, which is enhanced by dyein due to different affinities for certain dyes.

This fact can be of use for producing patterned effects. The local action of the swelling means can be done by applying to the fabric directly. by printing, blowing or painting, reserves with or without thickening means. and the fibre material is subsequently immersed in the swelling means. Dyestuffs can be added to the reserves, by which a local color effect can be produced together with the reserve.

The process can be used on all kinds of material made of artificial fibres consisting of regenerated cellulose. Materials made of artificial silk mixed with natural vegetable and animal fibres can be thereby treated.

In treating mixed materials it has been discovered, that it is advantageous for producing soft eiIects if the natural fibres, such for example as cotton, are worked up in the grey condition and are only cleaned or bleached after the local action of the swelling agents thereupon. By this means the end is attained that the natural fibres, in consequence of their natural incrustations, are not so quickly afiected by the swelling agents, 1. e., are not affected during the time required for altering the regenerated fibres, and therefore retain their original construction. If artificial fibres and both raw and already disintegrated natural fibres are employed side by side in mixed fibres, the variety of the effects is further increased, a result that makes itself evident particularly in subsequent dyeing.

Where in the appended claims I use the term artificial silk" I wish to be understood as including regenerated cellulose in the form of fibres, threads or fabric, and whether or not, in the case of threads, they also contain cotton or other fibres; and whether or not, in the case of fabric, it also contains cotton or other threads. Also I wish to be understood by the term "artificial silk fabric as used in the claims, to include fabrics made either wholly of regenerated cellulose fibres or of mixtures of same with other fibres.

. Such features of my invention as to product and process, not herein claimed, will be the subject of one or more copending divisional applications.

Having thus described an! invention, what I claim as new and desire to secure by Letters Patent, is:

1. Process for producing a novel character of artificial silk, which comprises subjecting the artificial silk to the action of a swelling agent which will chemically structurally change the same to effect a change in at least one of its natural physical characteristics:--lustre. stiffness, translucency, said treament being of sufiicient severity" tov effect said change but less than that capable of producing any substantial swelling action'on natural cotton fibres.

2. Process for producing a novel character of artificial silk, which comprises subjecting the artificial silk to the action of a swelling agent which will modify its characteristic lustre and increase its stiffness, said treatment being of sufficient severity to effect said change but less than that capable of producing any substantial swelling action on natural cotton fibres.

3. Process for producing a novel character of artificial silk, which comprises subjecting the artificial silk to the action of a swelling agent which will modify its characteristic lustre and render it stiffer more translucent, said treatment being of sufilcient "severity to effect said change but less than that capable of producing any substantial swelling action on natural cotton fibres. i

4. Process for eliminating the characteristic high lustre of artificial silk, which comprises subjecting the same to the action of alkali hydroxide of lustre-eliminating strength. said treatment being of sufiicient severity" to eflect said change but less than that capable of producing any substantial swelling action on natural cotton fibres.

5. Process for producing pattern effects on artificial silk fabric, which comprises subjecting localized portions of the fabric acording to pattern to the action of a swelling agent which will chemically structurally modify at least one of the characteristicsz-lustre, stiffness, translucency, so as to produce said pattern effect by contrast with the untreated portions, said treatment being of sufficient severity" to effect said change but less than that capable of producing any substantial swelling action on natural cotton fibres.

6. Process for producing pattern effects on artificial silk fabric, which comprises subjecting localized portions of the fabric according to'pattern to the action of a swelling agent which will modify the affinity of said portions for certain dyes, said treatment being of suflicient severity" to effect said change but less than that capable of producing any substantial swelling action on natural cotton fibres, and then dyeing the fabric to thereby produce different color tones in the treated and untreated portions.

7. The process of delusterizing the regenerated cellulose fibre. which comprises subjecting the same to the action of an alkali of delustering strength and subsequently neutralizing the remaining alkali.

8. The p of ornamenting the regenerated cellulose, rinting thereon with a paste in the desired pattern and subsequently subjecting said fabric to a bath, said paste or said bath including a caustic alkali.

9. A method for producing stiff fabrics that stand washing, which consists in manufacturing a mixed fabric composed of artificial silk fibres and of other fibres, and subjecting the mixed fabric to the action of an inorganic acid until the desired stiifcning of the artificial silk is obtained, leaving the vegetable fibres soft and pliable.

10. The method for producing stiff fabrics that stand washing, which consists in manufacturing a mixed fabric composed of artificial silk fibres and other fibres and subjecting the mixed fabric to the action of a cooled inorganic acid until the desired stifiening of the artificial silk is obtained, leaving the vegetable fibres soft and pliable.

ll. A method for producing stiff fabrics that stand washing, which consists in manufacturing a mixed fabric composed of artificial silk fibres and of vegetable fibres, and subjecting the mixed fabric to the action of an inorganic acid at atmospheric temperature until the desired stiffening of the artificial silk is obtained, leaving the vegetable fibres soft and pliable.

12. A stifi fabric that stands washing comprising a mixed fabric containing stiffened artificial silk and substantially unstiifened admixed threads.

l3. The method of producing stiif, washable fabrics, which comprises manufacturing a mixed fabric containing artificial silk, and subjecting the fabric to the action of mineral acid. the concentration of the acid, the duration and temperature at which the fabric is subjected to said acid being such as to harden the artificial silk without materially affecting the other constituents of the fabric. I

14. Artificial silk which has been subjected to the action of a swelling agent to structurally change the same and having at least one oi its natural physical characteristics:lustre, stillness. translucency, thereby altered, the treatment being of sumcient severity to eifect said change but less than that capable of producing any substantial swelling action on natural cotton fibres.

15. Artificial silk which has been subjected to the action of a swelling agent to structurally change the same, having less lustre than the original silk and having at least one of its characteristicsz-viz. stiifness, translucency, thereby altered, the treatment being of sufllcient severity to effect said change but less than that capable of producing any substantial swelling action on natural cotton fibres.

16. Artificial silk fabric with a pattern effect having localized portions which have been subjected to the action of a swelling agent to structurally change the same and having at least one of its natural physical characteristics:-lustre. stillness, translucency, thereby altered, the treatment being of sufilcient severity to eifect said change but less than thatcapable of producing any substantial swelling action on natural cotton fibres.

GEORGES HEBERLEIN.

CERTIFICATE OF CORRECTION.

Patent No. 1,998,576. April.23,l93$.

GEORGES HEBERLEIN.

It is hereby certified that error appears in the printed specification of the above numbered patent. requiring correction as follows: Page 2, first column, line 29, after the word "with" insert the word the; page 3, first column, line 71. claim I, for "treament" read treatment; second column, line 62, claim 9, for "vegetable" read othe line 64, claim 10, for "The" read A; and line 67, for "other" read vegetable; and that the said Letters Patent should be read with theae corrections therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 25th day .of lens, A. D. 1935.

Bryan M. Battey (lea!) Acting Commissioner of 1am. 

